US 2004O105899A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2004/0105899 A1 DOWodle et al. (43) Pub. Date: Jun. 3, 2004

(54) SOLVENT EXTRACTION PROCESS (30) Foreign Application Priority Data (76) Inventors: Paul Alan Dowdle, Sutton St Helens Nov. 6, 2000 (GB)...... OO27047.0 Merseyside (GB); Stuart Corr, Dec. 7, 2000 (GB)...... OO29969.3 Appleton Cheshire (GB); Helen Harris, O O Widnes Cheshire (GB) Publication Classification 7

Correspondence Address: 8. s ------All:

Andrew G Kolomayets O X O -- O ------Cook Alex McFarron Manzo Cummings & (57) ABSTRACT Mehler A proceSS for extracting a compound or composition of Suite 2850 matter from a raw material containing that compound or 200 West Adams Street composition as a constituent part is described. The process Chicago, IL 60606 (US) comprises the steps of (1) contacting the raw material with an extraction Solvent comprising a heptafluoropropane So as to extract the compound or composition from the raw (21) Appl. No.: 10/415,861 material into the Solvent, and (2) separating the Solvent containing the extracted compound or composition from raw (22) PCT Filed: Nov. 6, 2001 material. The process is particularly adapted for extracting flavours, fragrances and neutraceuticals from materials of (86) PCT No.: PCT/GB01/04904 plant origin. US 2004/0105899 A1 Jun. 3, 2004

SOLVENT EXTRACTION PROCESS matter from a raw material containing that compound or 0001. The present invention relates to a solvent extraction composition as a constituent part, which proceSS comprises proceSS in which a raw material containing a particular the steps of (1) contacting the raw material with an extrac compound or composition is treated with an extraction tion Solvent comprising a heptafluoropropane, e.g. 1,1,1,2, Solvent So as to remove at least a proportion of that com 3,3,3-heptafluoropropane (R-227ea), So as to extract the pound or composition from the raw material. compound or composition from the raw material into the Solvent and (2) separating the Solvent containing the 0002 Processes for extracting a desired compound or extracted compound or composition from the raw material. composition from a raw or bulk material which contains that compound or composition as a constituent part using an 0007. It will be appreciated that the process of the present extraction Solvent are known in the art. In these known invention will not necessarily extract all of the desired processes, the raw material is contacted with the extraction compound or composition that is contained in the raw Solvent, often under vigorous mixing conditions So as to material. facilitate the dissolution of the desired compound or com position into the extraction Solvent, and the resulting Solvent 0008. In one particular embodiment, the extraction pro liquor containing the desired compound or composition is ceSS of the present invention can be used to extract a natural then Separated from the raw material for Subsequent pro product from a plant material containing that product. cessing, e.g. distillation to remove the extraction Solvent. 0009. Accordingly, the present invention provides a pro Multiple extractions may Suitably be carried out on the same ceSS for extracting a natural product from a plant material raw material Sample So as to maximise the amount of the containing that product as a constituent part, which process desired compound or composition which is extracted from comprises the steps of (1) contacting the plant material with that Sample. Typical examples of extraction Solvents which an extraction Solvent comprising a heptafluoropropane So as have been used in the prior art extraction processes include to extract the natural product from the plant material into the hexane, methyl acetate, ethyl acetate, acetone and methanol. Solvent, and (2) separating the Solvent containing the 0.003 Although solvent extraction processes are used on extracted natural product from the plant material. a commercial Scale, the extraction Solvents which are cur rently used in these processes are not wholly Satisfactory. 0010 When used in this specification, the expression Thus, when Solvents Such as hexane are used to extract “plant material” not only includes materials which are flavoured or aromatic oils, Such as are used in the food and essentially unprocessed and as Such are clearly recognisable cosmetic industries, from plant matter containing those oils, as being of plant origin, for example bark, leaves, flowers, unwanted materials contained in the plant, e.g. high molecu roots and Seeds, but also materials, which although origi lar weight waxes, tend to be eluted along with the desired nating from plants, have been Subjected to various processes oil. This problem necessitates Subjecting the resultant heX and as Such have a form which is somewhat different than ane liquor or product concentrate to further processing in the plants from which they originated, for example ground, which the unwanted components are removed by extraction, dried roots or Seeds, Such as ground cumin and ground e.g. using ethanol. Furthermore, the extraction Solvents ginger, and expressed oils. which are currently in use have fairly high boiling points, and the elevated temperatures which are employed in the 0011. In a particularly preferred embodiment, the process distillation process to remove these high boiling Solvents of the present invention is used to obtain an extract, Such as from the extracted material can cause problems. For an essential oil, a concrete or an oleoresin, especially an example, the flavoured or aromatic oils contained in certain essential oil, comprising one or more flavour and/or fra plants are complex Substances containing a large number of grance compounds (hereinafter referred to collectively as individual compounds Some of which are relatively lo organoleptic compounds) from a plant material. Volatile or relatively thermally unstable. Consequently, high 0012. By the term “essential oil” we include oils which distillation temperatures can tend to result in a loSS of contain, inter alia, one or more terpenes and one or more product either through co-evaportion of the more volatile desired organoleptic compounds, Such as the oxygen con compounds with the extraction Solvent or thermal degrada taining terpenoids. Suitable essential oils which may be tion of the more thermally unstable compounds. extracted in accordance with the process of the present 0004. The use of hydrofluorocarbons such as 1,1,1,2- invention include citrus peel oils, Such as orange, lemon, tetrafluoroethane (R-134a) for extracting products Such as lime and grapefruit, peppermint, lavandin, rosemary oil and flavours and fragrances from materials of natural origin is celery Seed oil. also known from EP-A-616821. 0013 Concretes are usually solid, waxy materials pro 0005 The present invention provides a new solvent duced by Solvent extraction of natural products. extraction process which can be used to extract a wide variety of compounds or compositions from raw or bulk 0014 Oleoresins are usually viscous, pasty materials materials of which they form a constituent part. In one produced by Solvent extraction of natural products. particular embodiment, the present invention provides a Solvent extraction process which is capable of extracting the 0015 The process of the present invention is particularly flavoured, functional or aromatic oils or components con Suitable for extracting flavoured and/or aromatic materials tained in certain plant or culture materials. A particular from ginger, Vanilla, cloves, Star anise and jasmine. characteristic of the present process is that it does make use 0016. In a further embodiment, the extraction process of of an adsorbent. the present invention can be used to extract a biologically 0006 According to the present invention there is pro active compound, Such as a pesticide, a neutraceutical or a Vided a process for extracting a compound or composition of pharmaceutical, or a precursor to Such a biologically active US 2004/0105899 A1 Jun. 3, 2004 compound from a raw material containing that compound or 0027 Still further suitable co-solvents may be selected precursor, Such as a plant material, a cell culture or a from the amides, Sulphoxides, alcohols, ketones, carboxylic fermentation broth. acids, carboxylic acid derivatives, inorganic acids and nitro compounds. 0.017. Accordingly, the present invention provides a pro ceSS for extracting a composition comprising a biologically 0028 Preferred amide co-solvents include the N,N'-di active compound or a precursor thereof from a raw material alkylamides and alkylamides, especially dimethylforma containing that composition as a constituent part, which mide and formamide. process comprises the steps of (1) contacting the raw mate rial with an extraction Solvent comprising a heptafluoropro 0029 Preferred sulphoxide co-solvents include the pane So as to extract the composition from the raw material dialkylsulphoxides, especially dimethylsulphoxide. into the Solvent, and (2) separating the Solvent containing the 0030 Preferred alcohol co-solvents include the aliphatic extracted composition from the raw material. alcohols, particularly the alkanols. Preferred alkanols are Selected from the Cle, particularly the C- alkanols, with 0.018 Suitable pesticides which may be extracted using methanol, ethanol, 1-propanol and 2-propanol being espe the extraction process of the present invention include cially preferred. insecticides Such as the pyrethroids. 0.019 Suitable pharmaceuticals which may be extracted 0031 Preferred ketone co-solvents include the aliphatic using the extraction process of the present invention include ketones, particularly the dialkyl ketones. A particularly antibiotics, antimicrobials, antifungals and antivirals, for preferred dialkyl ketone is acetone. example the penicillins, the alkaloids, paclitaxel, monensin 0032 Preferred carboxylic acid co-solvents include for and cytochalasin. Precursors to these compounds may also mic acid and acetic acid. be extracted using the extraction process of the present invention. 0033 Preferred carboxylic acid derivatives for use as co-Solvents include the anhydrides, especially acetic anhy 0020 Suitable neutraceuticals that may be extracted dride, and the C, particularly the C- alkyl esters of C, include dietary Supplements Such as antioxidants and Vita particularly C- alkanoic acids, especially ethyl acetate. mins. 0034 Preferred nitro compounds for use as co-solvents 0021. The heptafluoropropane which is employed in the include the nitroalkanes and nitroaryl compounds, with process of the present invention may be 1,1,1,2,3,3,3-hep nitromethane and nitrobenzene being especially preferred. tafluoropropane (R-227ea) or 1,1,1,2,2,3,3-heptafluoropro pane (R-227ca). Mixtures of the two heptafluoropropanes 0035. The extraction solvent typically comprises from may also be employed. The preferred heptafluoropropane is 50.0 to 100% by weight, e.g. from 50.0 to 99.5% by weight, 1,1,1,2,3,3,3-heptafluoropropane (R-227ea). of a heptafluoropropane and from 0 to 50% by weight, e.g. from 0.5 to 50% by weight, of a co-solvent. Preferred 0022. The extraction solvent which is used in the process extraction solvents comprise from 70.0 to 100.0% by of the present invention may also comprise a co-Solvent in weight, e.g. from 70.0 to 99.0% by weight, of the heptafluo addition to the heptafluoropropane. ropropane and from 0 to 30% by weight, e.g. from 1 to 30% by weight, of the co-solvent. Particularly preferred extrac 0023 Suitable co-solvents will typically have a boiling tion solvents comprise from 80.0 to 100.0% by weight, e.g. point of 80 C. or below, for example in the range of from from 80.0 to 98.0% by weight, of the heptafluoropropane -85 to 80° C. The preferred co-solvents have a boiling point and from 0 to 20.0% by weight, e.g. from 2.0 to 20.0% by of 60° C. or below, for example in the range of from -85 to weight, of the co-Solvent. 60° C., preferably 20 C. or below, for example in the range of from -70 to 20° C., and more preferably 10° C. or below, 0036). If the co-solvent is a flammable material, then the for example in the range of from -60 to 10° C. Mixtures of extraction solvent will preferably comprise sufficient of the two or more co-Solvents may be used if desired. heptafluoropropane to render it non-flammable overall. Where the extraction solvent is a blend of one or more 0024. The co-solvent is also preferably fluorine-free and compounds, the resulting blend may be Zeotropic, azeotropic more particularly halogen-free. or azeotrope-like. 0.025 Preferred co-solvents may be selected from the 0037. The extraction solvent which is used in the process Cle, particularly the C. hydrocarbon compounds by which of the present invention may be in liquid, gaseous or we mean compounds containing only carbon and hydrogen vaporous form, but is preferably in liquid form. Since both atoms. Suitable hydrocarbons may be aliphatic or alicyclic. heptafluoropropanes have boiling points below room tem Preferred hydrocarbons are the alkanes and cycloalkanes, perature, maintaining the Solvent in liquid form will involve with alkanes Such as ethane, n-propane, i-propane, n-butane the application of cooling and/or Super-atmospheric pres and i-butane being especially preferred. SUCS. 0026. Other preferred halogen free co-solvents include 0038. The preferred extraction solvents comprise only the hydrocarbon ethers, by which we mean compounds low boiling materials so that removal of the solvent from the having the formula R'-O-R in which R" and R are Solvent liquor containing the extract tends to be relatively independently hydrocarbyl groups containing only carbon facile allowing the distillation to be carried out at relatively and hydrogen atoms, Such as C. and preferably C- alkyl low temperatures, e.g. room temperature and below. This, in groups. Preferred dialkyl ethers include dimethyl ether, turn, reduces the risk of loosing desired product either methyl ethyl ether and diethyl ether. through co-evaporation of the more volatile compounds with US 2004/0105899 A1 Jun. 3, 2004

the extraction Solvent or thermal degradation of the more raw material Sample to a Succession of individual extrac thermally unstable compounds. tions. Once the raw material Sample is exhausted, it is then 0.039 The raw material which is subjected to the present removed from the extraction vessel and replaced with a fresh extraction process may be a liquid, e.g. a Solution, Suspen raw material Sample. Sion or emulsion, or a Solid. If the raw material is a Solid, 004.5 The present invention is now illustrated but not then the efficiency of the extraction process may be signifi limited by the following examples. cantly improved by reducing the Solid to a finely divided 0046 All the examples relate to the extraction of natural form, Such as a powder. products. 0040. The extraction process of the present invention 0047 General procedures A, B and C relate to the extrac may be conducted at the Supercritical temperature of the tion of Solid materials. General procedure D relates to the extraction Solvent, in which case elevated temperatures will extraction of liquids. need to be employed. Preferably, however, the extraction proceSS is conducted at a temperature in the range of from 0048. In Examples 1 to 7 and 27 to 40, the extracts that -60 to 150 C., more preferably in the range of from -40 to were obtained are of interest primarily as a flavour and/or a 60° C. and particularly in the range of from -30 to 40 C. fragrance. 0041. The extraction process of the present invention 0049. In Examples 8 to 26, the extracts that were obtained may be conducted at atmospheric or Super-atmospheric are of interest primarily as neutraceuticals. preSSures. The precise operating pressure will depend, inter 0050. In referring to the yield of the extract, we are alia, on the extraction Solvent which is used, particularly its referring to the weight of the extract obtained expressed as boiling point, and whether the extraction proceSS is to be a percentage of the weight of the original natural product conducted with that Solvent in liquid or gaseous form. Preferred operating preSSures are in the range of from 0.1 to biomass that was Subjected to the extraction. 200 bar, more preferably in the range of from 0.5 to 30 bar and particularly in the range of from 1 to 15 bar. General Procedure A 0042. The contacting of the extraction solvent with the 0051) Approximately 40 g of the natural product to be raw material to be processed may be carried out under extracted was weighed into a cellulose SOXhlet extraction Vigorous mixing conditions So as to facilitate the dissolution thimble. The cellulose thimble containing the natural prod of the material to be extracted into the extraction Solvent. uct was then placed in a glass SOXhlet eXtractor and a The Vigorous mixing may be achieved by mechanically pre-weighed receiver flask was attached in position on the Shaking the extraction vessel containing the raw material/ extractor. The extractor was then placed in an autoclave, extraction Solvent mixture, by Stirring that mixture or by the equipped with a cold finger condenser, and the autoclave application of ultraSonic excitation. was Sealed and evacuated. 0052 Approximately 330 g of 1,1,1,2,3,3,3-heptafluoro 0043. After the extraction process of the present inven propane (R-227ea) was transferred from a cylinder into the tion has been completed, the Solvent liquor containing the autoclave via a ball valve which was then resealed. The extract can be distilled to remove the extraction Solvent from transfer of Solvent into the autoclave raised the preSSure in the extract. The resulting extract may then be used as it is or, the autoclave. The bottom section of the autoclave was then alternatively, it may be Subjected to one or more further heated to about 50° C. with a hot air gun and cooling fluid processes, for example to purify the extract or to isolate a was passed through the cold finger condenser to lower the given compound or compounds contained in the extract. temperature of the cold finger to about -10°C. The extrac 0044) The extraction process of the present invention tion was allowed to proceed for a few hours and during this may be operated continuously with the same extraction time the temperature and pressure were monitored to ensure Solvent being used repeatedly. A Suitable installation for that 15 barg was not exceeded. The solvent refluxes within carrying out a continuous extraction proceSS typically com the SOXhlet extractor and Solvent condensing on the cold prises an extraction vessel, a distillation unit, a compressor, finger drops through the contents of the thimble and into the a condenser and a Suitable arrangement of connecting pipe receiver flask. work. The extraction Solvent is first charged to the extraction vessel where it is contacted with the raw material to be 0053) On completion of the extraction, the solvent was processed, possibly under vigorous mixing conditions So as reclaimed by opening the ball valve and condensing the to facilitate the dissolution of the compound or composition solvent into a cooled Whitey Bomb. When the pressure in to be extracted into the extraction Solvent. The resulting the autoclave reached atmospheric, the autoclave was Solvent liquor containing the extract is then Separated from opened and the SOXhlet extractor retrieved. The receiver the raw material, e.g. by allowing the liquor to drain through flask containing the extracted material was then detached a filter arranged at the bottom of the extraction vessel, and and re-weighed to determine the yield. passed to the distillation unit where the extraction Solvent is 0054 Asample of the extracted material was then analy removed by evaporation to leave the extract. The vapour Sed by gas chromatography/mass spectrometry (GC/MS) to generated in the distillation unit is compressed, e.g. using a determine its composition. No correction for individual diaphragm compressor, and is then delivered to a condenser component response factors was made. The gas chromato which returns the extraction solvent to liquid form for gram was a Perlin-Elmer AutoSystem XL coupled to a recharging to the extraction vessel. With a continuous Perkin Elmer Q-Mass 910 mass detector and a flame ioni extraction process of this kind, it is possible to maximise the sation detector. The machine was equipped with a amount of the extract obtained without Subjecting the same Chrompack CPSIL 5 column of 50 m length. During the US 2004/0105899 A1 Jun. 3, 2004

analysis, the column temperature was set at 200 C. and held General Procedure C at this temperature for 30 minutes. The injector temperature was set at 300° C. and the flame ionised detector set at 150 0061 The natural product to be extracted was weighed into a cellulose SOXhlet eXtraction thimble and ethanol was C. then added at a loading of 10% by weight on the weight of 0.055 Asample of the extracted material was also sent for the natural product biomass. The cellulose thimble contain sensory evaluation. The sample was diluted to 2% w/w in ing the natural product biomass and ethanol was then placed i-propyl alcohol and this diluted material was then added to in a glass SOXhlet extractor and a pre-weighed receiver flask a suitable quantity of a syrup (specification: 4 Brix; 150 was attached in position on the extractor. The extractor was ppm benzoic acid) which had been previously prepared by then placed in an autoclave, equipped with a cold finger dissolving 199.91 kg of granular Sugar and 0.89 kg of condenser, and the autoclave was Sealed and evacuated. sodium benzoate (preservative) in 1000 litres of water. The 0062) Approximately 340 g of 1,1,1,2,3,3,3-heptafluoro resulting composition was then further diluted with water at propane (R-227ea) was transferred from a cylinder into the a ratio of 1 part to 4 parts water. autoclave via a ball valve which was then resealed. The 0056. The prepared sample was then evaluated by an transfer of Solvent into the autoclave raised the preSSure in expert taste panel against Selected reference materials. The the autoclave. The bottom section of the autoclave was then reference materials were based on the naturally occurring heated to about 50 C. with a heated water jacket and constituents of the natural product in question and were cooling fluid was passed through the cold finger condenser classified into groups by the expert panel. The comments of to lower the temperature of the cold finger to about 10 C. the panel on the organoleptic characters of the extracts were The extraction was allowed to proceed for four hours and collected. during this time the temperature and pressure were moni tored to ensure that 15 barg was not exceeded. The solvent General Procedure B refluxes within the SOXhlet extractor and Solvent condensing 0057 The natural product to be extracted was weighed on the cold finger drops through the contents of the thimble into a cellulose Soxhlet extraction thimble. The cellulose and into the receiver flask. thimble containing the natural product was then placed in a 0063. On completion of the extraction, the R-227ea sol glass SOXhlet eXtractor and a pre-weighed receiver flask was vent was reclaimed by opening the ball valve and condens attached in position on the extractor. The extractor was then ing the solvent into a cooled Whitey Bomb. When the placed in an autoclave, equipped with a cold finger con preSSure in the autoclave reached atmospheric, the autoclave denser, and the autoclave was Sealed and evacuated. was opened and the Soxhlet extractor retrieved. The receiver 0.058 Approximately 340 g of 1,1,1,2,3,3,3-heptafluoro flask containing the extracted material and ethanol Solvent propane (R-227ea) was transferred from a cylinder into the was then detached and the ethanol removed on a rotary autoclave via a ball valve which was then resealed. The evaporator. The receiver flask was then re-weighed to deter transfer of Solvent into the autoclave raised the preSSure in mine the yield. the autoclave. The bottom section of the autoclave was then heated to lo about 50° C. with a heated water jacket and General Procedure D cooling fluid was passed through the cold finger condenser to lower the temperature of the cold finger to about 10 C. 0064. This is a liquid-liquid extraction. The extraction was allowed to proceed for four hours and 0065. The liquid natural product to be extracted was during this time the temperature and pressure were moni weighed into a glass liquid-liquid extraction vessel of the tored to ensure that 15 barg was not exceeded. The solvent type that is conventionally used in the laboratory with heavy refluxes within the SOXhlet extractor and Solvent condensing Solvent phases. A pre-weighed receiver flask was attached in on the cold finger drops through the contents of the thimble position on the extraction vessel. The extraction vessel was and into the receiver flask. then placed in an autoclave, equipped with a cold finger 0059 On completion of the extraction, the solvent was condenser, and the autoclave was Sealed and evacuated. reclaimed by opening the ball valve and condensing the 0066 Approximately 340 g of 1,1,1,2,3,3,3-heptafluoro solvent into a cooled Whitey Bomb. When the pressure in propane (R-227ea) was transferred from a cylinder into the the autoclave reached atmospheric, the autoclave was autoclave via a ball valve which was then resealed. The opened and the SOXhlet extractor retrieved. The receiver transfer of Solvent into the autoclave raised the preSSure in flask containing the extracted material was then detached the autoclave. The bottom section of the autoclave was then and re-weighed to determine the yield. heated to about 50 C. with a heated water jacket and 0060. Where indicated, a sample of the extracted material cooling fluid was passed through the cold finger condenser was then analysed by gas chromatography/mass spectrom to lower the temperature of the cold finger to about 10 C. etry (GC/MS) to determine its composition. No correction The extraction was allowed to proceed for two or four hours for individual component response factors was made. The and during this time the temperature and pressure were gas chromatogram was a Perkin-Elmer AutoSystem EL monitored to ensure that 15 barg was not exceeded. The coupled to a Perkin Elmer Q-Mass 910 mass detector and a Solvent refluxes within the extraction vessel and solvent flame ionisation detector. The machine was equipped with a condensing on the cold finger drops into the extraction Chrompack CPSIL 5 column of 50 m length. During the vessel and then into the receiver flask. analysis, the column temperature was set at 200 C. and held 0067. On completion of the extraction, the solvent was at this temperature for 30 minutes. The injector temperature reclaimed by opening the ball valve and condensing the was set at 300° C. and the flame ionised detector set at 150 solvent into a cooled Whitey Bomb. When the pressure in C. the autoclave reached atmospheric, the autoclave was US 2004/0105899 A1 Jun. 3, 2004 opened and the liquid-liquid extraction vessel retrieved. The receiver flask containing the extracted material was then detached and re-weighed to determine the yield. Eugenol 57.59 wt.% Caryophyllene 16.89 wt.% EXAMPLE 1. C-Caryophyllene O.53 wt.% 0068. In this example, general procedure A described Eugenol acetate 25.0 wt.% above was used to extract chopped dried ginger. The extrac tion was continued for 4.5 hours. 0081. The sensory evaluation of the liquid clove extract 0069. A yellow/orange translucent liquid was obtained at was made against eugenol, iso-eugenol, eugenyl acetate and a yield of 4.03%. The GC/MS analysis showed that the clove terpenes. liquid had the following composition. 0082 The extract was classified as follows: 0083 Eugenol, slight phenolic, slight petrol, iso Pinene 0.12 wt.% Camphene 1.12 wt.% eugenol, Sweet, balsamic, terpenic. Phelanderene 0.21 wt.% Limonene 0.02 wt.% EXAMPLE 4 Sabiene 2.89 wt.% Eucalyptol O.O5 wt.% 0084. In this example, general procedure A described Cedrene 14.75 wt % Caryophyllene/Farnesene 19.06 wt.% above was used to extract ground Star anise. The extraction Zingibrene 56.55 wt.% was continued for 2 hours. Bisabolene 5.23 wt.% 0085. A pale yellow/green oil was obtained at a yield of 5.77%. The GC/MS analysis showed that the oil had the 0070 The sensory evaluation of the liquid ginger extract following composition. was made against the following reference materials. 0071 (i) Earthy notes-Camphene, Bornyl acetate Limonene 1.74 wt.% 0.072 (ii) Citrus notes-Citral p-anisaldehyde O.39 wt.% 0073 (iii) Floral notes-Linalool, Geraniol p-allylanisole 97.87 wt.% 0074 (iv) Spicy notes-Zingerone, Bisabolene 0086 The sensory evaluation of the oily star anise extract 0075) The extract was classified as follows: was made against anethole and anisaldehyde. 0076 Strong floral/lemon character. High (warm) Spice notes. Medium to high heat. Low earthy char 0087. The extract was classified as follows: acter. Some phenolic notes. 0088 Clean anethole. Sweet. EXAMPLE 2 EXAMPLE 5 0077. In this example, general procedure A described above was used to extract chopped Vanilla pods. The Vanilla 0089. In this example, general procedure A described pods were chopped into approximately 3 mm pieces and the above was used to extract jasmine. Jasmine concrete (11.4 g) pieces placed in the extraction thimble for extraction in was melted and loaded onto a particulate Vermiculite Support accordance with the general procedure. The extraction was (4.5 g). The jasmine coated Vermiculite was then charged to continued for 4.5 hours. the extraction thimble and the extraction conducted in 0078. A pale yellow solid was obtained at a yield of accordance with the general procedure. The extraction was 2.83%. The GC/MS analysis showed that the extract had the continued for 5.25 hours. following composition. 0090. A yellow translucent liquid was obtained at a yield of 41.32%. The GC/MS analysis showed that the liquid had the following composition. 4-hydroxybenzaldehyde O.78 wt.% Vanillin 99.22 wt.% Linalool 24.42 wt.% Benzyl acetate 63.29 wt.% EXAMPLE 3 Indole 1.15 wt.% Eugenol 4.5 wt.% 0079. In this example, general procedure A described Jasmone 3.91 wt.% C-Farnesene 1.13 wt.% above was used to extract ground cloves. The extraction was Unknown 1.6 wt.% continued for 2 hours. 0080 A pale yellow translucent liquid was obtained at a yield of 9.59%. The GC/MS analysis showed that the liquid 0091. The sensory evaluation of the liquid jasmine had the following composition. extract was made against the following reference materials. US 2004/0105899 A1 Jun. 3, 2004

0092 Floral notes EXAMPLE 12 0093 Geraniol (rosey/turkish delight) 0114. In this example, general procedure B described above was used to extract 50.95 g of ground, dried soya 0094) Linalool (rosey) beans. 0.095 Phenyl ethyl alcohol (aromatic floral/honey 0.115. A colourless liquid was obtained at a yield of like) 1.57%. 0096). Other EXAMPLE 13 O097 Indole (animal-like) 0116. In this example, general procedure B described 0098 Cis-Jasmonate (jasmone) above was used to extract 50.0 g of powdered valerian root. 0117. A yellow, waxy oil was obtained at a yield of 0.9%. 0099 Benzyl acetate (fruity) EXAMPLE 1.4 0100. The extract was classified as follows: 0118. In this example, general procedure B described 0101 Strong floral (PEA) with strong jasmone and above was used to extract 50.05 g of dried, powdered St benzyl alcohol. Slight rosey (linalool) with some John's Wort flower. fruity character. 0119) A yellow, waxy material was obtained at a yield of EXAMPLE 6 2.4%. 0102) In this example, general procedure A described EXAMPLE 1.5 above was used to extract ground coffee. The extraction was 0120 In this example, general procedure B described continued for four hours. above was used to extract 40.0 g of dried, powdered Echina 0103) A yellow/orange solid was obtained at a yield of cea flower. 3.6%. 0121 White foam like droplets were obtained at a yield of 3.0%. EXAMPLE 7 0104. In this example, general procedure A described EXAMPLE 16 above was used to extract ground patchouli leaf. The extrac 0122) In this example, general procedure B described tion was continued for four hours. above was used to extract 35.1 g of dried, powdered ginkgo 0105. A pale yellow, translucent liquid was obtained at a biloba. yield of 11.15%. 0123. An orange, waxy oil was obtained at a yield of 3.14%. EXAMPLE 8 0106. In this example, general procedure B described EXAMPLE 1.7 above was used to extract 29.9 g of dried, ground rosemary 0.124. In this example, general procedure B described leaves. above was used to extract 69.7 g of dried, powdered Panax 0107 A yellow/orange, waxy oil was obtained at a yield ginseng root. of 4.18%. 0.125. A slightly yellow oily material was obtained at a yield of 1.87%. EXAMPLE 9 0108. In this example, general procedure B described EXAMPLE 1.8 above was used to extract 50.05 g of green tea leaves. 0.126 In this example, general procedure C described above was used to extract 30.05 g of dried, ground rosemary 0109) A green/orange solid was obtained at a yield of leaves. 2.5%. 0127. A yellow/orange, translucent liquid was obtained at EXAMPLE 10 a yield of 1.35%. 0110. In this example, general procedure B described EXAMPLE 1.9 above was used to extract 49.9 g of black tea leaves. 0128. In this example, general procedure C described 0111. A dark green solid was obtained at a yield of 2.2%. above was used to extract 50.55g of green tea leaves. EXAMPLE 11 0129. A dark green liquid was obtained at a yield of O.36%. 0112) In this example, general procedure B described above was used to extract 60.0 g of ground turmeric. EXAMPLE 2.0 0113 A pale orange, translucent liquid was obtained at a 0.130. In this example, general procedure C described yield of 4.58%. above was used to extract 49.95 g of black tea leaves. US 2004/0105899 A1 Jun. 3, 2004

0131) A dark green liquid was obtained at a yield of EXAMPLE 28 O.23%. 0151. In this example, general procedure B described EXAMPLE 21 above was used to extract 1.75 g of oakmoSS concrete. 0152. A colourless, fragrant oil was obtained at a yield of 0.132. In this example, general procedure C described 45.7%. above was used to extract 60.01 g of ground turmeric. 0.133 An orange, translucent liquid was obtained at a EXAMPLE 29 yield of 3.68%. 0153. In this example, general procedure B described above was used to extract 0.62 g of broom concrete. EXAMPLE 22 0154) A colourless, fragrant oil was obtained. 0134. In this example, general procedure C described above was used to extract 50.35 g of ground, dried Soya EXAMPLE 30 beans. O155 In this example, general procedure B described 0135) A pale yellow, oily emulsion was obtained at a above was used to extract 43.9 g of ground West African yield of 0.84%. cocoa beans. 0156 A white, waxy Solid having an intense cocoa fra EXAMPLE 23 grance was obtained at a yield of 2.0%. 0136. In this example, general procedure C described EXAMPLE 31 above was used to extract 49.35 g of powdered valerian root. O157. In this example, general procedure B described 0.137. A dark green/brown liquid was obtained at a yield above was used to extract 44.1 g of ground Indian black of 0.71%. pepper. EXAMPLE 24 0158. A pale yellow oil with white solids was obtained at a yield of 5.0%. 0.138. In this example, general procedure C described above was used to extract 49.9 g of dried, powdered St 0159. A GC/MS analysis was conducted on the compo John's Wort flower. Sition. The composition contained the following compo nentS. 0.139. A dark green liquid was obtained at a yield of 2.8%. 0160 O-Pinene EXAMPLE 25 0161 Sabinene 0140. In this example, general procedure C described 0162 B-Pinene above was used to extract 40.1 g of dried, powdered Echina 0163 3-Carene cea flower. 0164) Limonene 0.141. A yellow, translucent liquid was obtained at a yield of 0.96%. 0165 B-Phellandrene 0166 Copaene EXAMPLE 26 0167 Caryophyllene 0142. In this example, general procedure C described above was used to extract 34.95g of dried, powdered ginkgo EXAMPLE 32 biloba. 0.168. In this example, general procedure B described 0143 A dark green liquid was obtained at a yield of above was used to extract 43.5g of ground pink pepper. 1.72%. 0169. A pale yellow oil with white solids was obtained at a yield of 5.5%. EXAMPLE 27 0170 A GC/MS analysis was conducted on the compo 0144. In this example, general procedure B described Sition. The composition contained the following compo above was used to extract 1.2 g of rose concrete. nentS. 0.145) A pink, fragrant oil was obtained at a yield of 8.0%. 0171 O-Pinene 0146 A GC/MS analysis was conducted on the oil. The 0172 Sabinene oil contained the following components. 0173 B-Myrcene 0147 Phenylethyl alcohol 0174 B-Pinene 0148 B-Citronellol 0175 O-Phellandrene 0149 Nerol 0176) 3-Carene 0150 Geraniol 0177 Limonene US 2004/0105899 A1 Jun. 3, 2004

0178 Linallyl acetate EXAMPLE 35 0179 B-Phellandrene 0210. In this example, general procedure B described above was used to extract 26.7 g of ground magnolia bark. 0180 Copaene 0211. A yellow oil was obtained at a yield of 5.6% 0181 Caryophyllene 0212. A GC/MS analysis was conducted on the oil. The 0182 Germacrene oil contained the following components. 0213 Caryophyllene EXAMPLE 33 0183 In this example, general procedure B described 0214 B-Selinene above was used to extract 31.65 g of ground Szechuan 0215 Caryophyllene oxide pepper. 0216) Eudesmol 0184. A pale yellow oil with crystalline solids was obtained at a yield of 4.6%. 0217 B-Eudesmol 0185. A GC/MS analysis was conducted on the compo EXAMPLE 36 Sition. The composition contained the following compo 0218. In this example, general procedure C described nentS. above was used to extract 1.45 g of rose concrete. 0186 C-Pinene 0219. A pink, fragrant oil was obtained at a yield of 3.6%. 0187 Sabinene EXAMPLE 37 0188 B-trans Ocimene 0220. In this example, general procedure C described 0189 p-Cymene above was used to extract 29.8g of ground magnolia bark. 0221) A yellow oil was obtained at a yield of 2.3%. 0190. Limonene 0191 B-Phellandrene EXAMPLE 38 0192 cis-Thujan-4-ol 0222. In this example, general procedure D described above was used to extract 33.9 g of Californian white 0193 Linalool grapefruit oil. The extraction was continued for 2 hours. 0194 Caryomenthone 0223) A pale yellow oil was obtained at a yield of 43.7%. The oil was paler in colour and had a stronger fruit aroma 0195 1-(4-hydroxy-3,5-dimethoxyphenyl)-etha than the original oil. OC EXAMPLE 39 EXAMPLE 34 0224. In this example, general procedure D described 0196. In this example, general procedure B described above was used to extract 42.8 g of Sicilian CP lemon oil. above was used to extract 12.2 g of crushed, dried mint The extraction was continued for 2 hours. leaves. 0225. A pale yellow oil was obtained at a yield of 84.6%. 0197) A pale green oil was obtained at a yield of 7.8%. The oil was paler in colour and had a stronger fruit aroma than the original oil. 0198 A GC/MS analysis was conducted on the oil. The oil contained the following components. EXAMPLE 40 0199 Eucalyptol 0226. In this example, general procedure D described above was used to extract 40.9 g of Mexican lime oil. The 0200 trans-Thujan-4-ol extraction was continued for 4 hours. 0201 p-Menthone 0227. An oil having similar properties to the original oil 0202) Isomenthone was obtained at a yield of 94%. 0203 Neomenthol 1. A process for extracting a compound or composition of matter from a raw material containing that compound or 0204 Menthol composition as a constituent part, which proceSS comprises 0205 Pulegone the steps of (1) contacting the raw material with an extrac tion Solvent comprising a heptafluoropropane So as to extract 0206 3-Carvomenthone the compound or composition from the raw material into the Solvent, and (2) separating the Solvent containing the 0207 Menthyl acetate extracted compound or composition from the raw material. 2. A proceSS as claimed in claim 1, wherein the raw 0208 B-FarneSene material is of plant origin and the composition to be 0209) Caryophyllene extracted is a flavour or a fragrance. US 2004/0105899 A1 Jun. 3, 2004

3. A proceSS as claimed in claim 2, wherein the flavour or 13. A proceSS as claimed in claim 12, wherein the co fragrance is comprised in an oil, a concrete or an oleoresin. Solvent comprises n-butane. 4. A proceSS as claimed in claim 1, wherein the compound or composition to be extracted from the raw material com 14. A process as claimed in claim 9, wherein the co prises a biologically active compound or a precursor thereof. Solvent comprises at least one hydrocarbon ether having the 5. A proceSS as claimed in claim 4, wherein the biologi formula R'-O-R in which R" and R are independently cally active compound is a pesticide or a precursor thereof. C-6 alkyl groups. 6. A proceSS as claimed in claim 4, wherein the biologi 15. A proceSS as claimed in claim 14, wherein the co cally active compound is a pharmaceutically active Sub Solvent comprises at least one ether Selected from dimethyl stance or a precursor thereof. ether, methyl ethyl ether and diethyl ether. 7. A proceSS as claimed in claim 4, wherein the biologi cally active compound is a neutraceutical or a precursor 16. A proceSS as claimed in claim 15, wherein the co thereof. Solvent comprises dimethyl ether. 8. A process as claimed in any one of the preceding 17. A process as claimed in claim 9, wherein the co claims, wherein the extraction Solvent comprises 1,1,1,2,3, Solvent comprises at least one compound Selected from the 3.3-heptafluoropropane (R-227ea). C. alkanols and the C- alkyl esters of C alkanoic acids. 9. A process as claimed in any one of the preceding 18. A proceSS as claimed in claim 17, wherein the co claims, wherein the extraction Solvent comprises a co Solvent is Selected from ethanol and ethyl acetate. Solvent in addition to the heptafluoropropane. 19. A process as claimed in any one of the preceding 10. A proceSS as claimed in claim 9, wherein the co Solvent comprises at least one C. hydrocarbon. claims, wherein the extraction Solvent is in liquid form. 11. A process as claimed in claim 10, wherein the C 20. A process as claimed in any one of the preceding hydrocarbon is Selected from the alkanes and cycloalkanes. claims which is conducted at a temperature in the range of 12. A process as claimed in claim 11, wherein the co from -60 to 150° C. Solvent comprises at least one compound Selected from ethane, n-propane, i-propane, n-butane and i-butane.